Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
  • C10M159/12—Reaction products
  • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/146—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings having carboxyl groups bound to carbon atoms of six-membeered aromatic rings having a hydrocarbon substituent of thirty or more carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/26—Overbased carboxylic acid salts
  • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/287—Partial esters
  • C10M2207/289—Partial esters containing free hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
  • C10M2215/064—Di- and triaryl amines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/28—Amides; Imides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
  • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
  • C10M2219/046—Overbasedsulfonic acid salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/045—Metal containing thio derivatives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/02—Groups 1 or 11
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/04—Groups 2 or 12
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/48—Slushing oils

Definitions

• the present invention relates to a lubricating oil additive and a lubricating oil composition, specifically, a lubricating oil additive and a lubricating oil composition into which two or more metal detergents are incorporated to exhibit good storage stability.
• Lubricating oils are required to have various performances in accordance with their use purposes.
• engine oils are required to have high thermal stability, high-temperature detergency, oxidization stability, wear prevention and others, and are produced by incorporating lubricating oil additives such as an anti-wear agent, an ashless dispersing agent, a metal detergent, and an antioxidant thereinto.
• lubricating oil additives such as an anti-wear agent, an ashless dispersing agent, a metal detergent, and an antioxidant thereinto.
• the metal detergent include such as salicylates, phenates and sulfonates. These are used alone or in combination in order to improve the high-temperature detergency and other properties of lubricating oils.
• patent document 1 Japanese Patent Application Laid-Open (JP-A) No. 8-176583
• patent document 2 JP-A No. 10-53784
• JP-A No. 10-53784 disclose diesel engine oil compositions into which a combination of metal detergents having different base numbers is incorporated.
• Patent document 2 paragraph (0010) specifically describes SAP 001, SAP 005, and SAP 007 manufactured by Shell Chemicals Japan and OSCA 435B and OSCA 463 manufactured by Osca Chemical as examples of a “highly basic calcium salicylate/magnesium salicylate”, and patent document 2, paragraph (0012) specifically describes SAP 002 manufactured by Shell Chemicals Japan and OSCA 431B manufactured by Osca Chemical as “low basic calcium salicylates”.
• the inventors have paid attention to the structure of a salicylate as a metal detergent, and made eager investigations to find out that in the case of using a combination of a salicylate having a specific structure and a metal detergent other than any salicylate, no precipitation is generated in the form of a lubricating oil additive or a lubricating oil composition so that a very good storage stability is exhibited.
• the present invention has been made.
• the present invention is a lubricating oil additive and a lubricating oil composition obtained by incorporating, into a lubricant base oil, (A) a salicylate detergent and (B) a metal detergent other than any salicylate detergent, wherein the salicylate detergent (A) is an alkali metal or alkaline earth metal salicylate represented by the general formula (1) and/or a (per)basic salt thereof:
• R 1 and R 2 may be the same or different and each represent a hydrocarbon group having 1 to 40 carbon atoms, the hydrocarbon group may contain oxygen or nitrogen, M represents an alkali metal or alkaline earth metal, and n is 1 or 2 in accordance with the valence of the metal.
• one of R 1 and R 2 in the general formula (1) is a hydrocarbon which has 10 to 40 carbon atoms, and the other is a hydrocarbon which has less than 10 carbon atoms (and may have oxygen or nitrogen) or R 1 and R 2 are each a hydrocarbon group having 10 to 40 carbon atoms.
• the lubricating oil additive and the lubricating oil composition of the present invention are particularly useful in the case where the metal ratio of the component (A) is 1.1 or more.
• the metal detergent (B) other than any salicylate detergent is at least one selected from alkali metal or alkaline earth metal sulfonates, alkali metal or alkaline earth metal phenates, and (per)basic salts thereof.
• the lubricating oil additive and the lubricating oil composition of the present invention further comprise at least one lubricating oil additive selected from (C) an anti-wear agent, (D) an ashless dispersing agent, and (E) an antioxidant.
• a mineral type base oil or synthetic type base oil that is used in ordinary lubricating oil can be used without any especial limit.
• the mineral oil type base oil examples include oils obtained by purifying a lubricating oil fraction yielded by distilling an atmospheric residue oil, which is obtained by distilling crude oil under normal pressure, under reduced pressure by at least one selected from solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, hydrorefining and other treatments; wax-isomerized mineral oils; and base oils produced by isomerizing GTL wax (gas-to-liquid wax).
• the synthetic type base oil include polybutene or hydrogenated products thereof; poly- ⁇ -olefins, such as 1-octene oligomer and 1-decene oligomer, or hydrogenated products thereof; diesters such as ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate and di-2-ethylhexyl cebacate; polyol esters such as trimethylolpropane caprilate, trimethylolpropane pelargonate, pentaerythritol-2-ethyl hexanoate, and pentaerythritol pelargonate; and aromatic synthesis oils such as alkylnaphthalene, alkylbenzene, and aromatic esters; and mixtures thereof.
• poly- ⁇ -olefins such as 1-octene oligomer and 1-decene
• the above-mentioned mineral oil type base oils, the above-mentioned synthetic type base oils, or any mixture composed of two or more lubricating oils selected therefrom can be used.
• examples thereof include one or more out of the mineral oil type base oils, one or more out of the synthetic type base oils, and a mixture of one or more out of the mineral oil type base oils and one or more out of the synthetic type base oils.
• the aromatic fraction content in the lubricant base oil is not particularly limited, and the content as % C A is preferably 10 or less, more preferably 3 or less, in particular preferably 2 or less by mass.
• the “% C A ” represents the percentage of the number of the aromatic carbon atoms to the number of all the carbon atoms, the percentage being obtained by ring analysis prescribed in ASTM D 3238.
• the kinematic viscosity of the lubricant base oil is not particularly limited, and the kinematic viscosity at 100° C. is preferably 20 mm 2 /s or less, more preferably 10 mm 2 /s or less in order to keep the low-temperature viscosity property good.
• the kinematic viscosity is preferably 1 mm 2 /s or more, more preferably 2 mm 2 /s or more in order to form a sufficient oil film at lubrication places, thereby keeping lubricity and further control the evaporation loss of the lubricant base oil into a low value.
• the evaporation loss quantity of the lubricant base oil is 20% or less by mass, more preferably 16% or less by mass, and in particular preferably 10% or less by mass as NOACK evaporation quantity.
• NOACK evaporation quantity of the lubricant base oil is kept at a value of 20% or less by mass, the evaporation loss of the lubricating oil can be controlled into a low value and further in the case of using the lubricating oil composition as a lubricating oil for internal combustion engine, it is possible to prevent sulfur compounds, phosphorus compounds or metals in the composition from being deposited together with the lubricant base oil on an exhaust gas purifying device so as to prevent a bad effect on the exhaust gas purifying performance in advance.
• the NOACK evaporation quantity referred to herein is measured in accordance with CEC L-40-T-87.
• the viscosity index of the lubricant base oil is not particularly limited, and the value thereof is preferably 80 or more, more preferably 100 or more, and even more preferably 120 or more to obtain a good viscometric property at temperatures from low temperature and high temperature.
• the component (A) in the invention is an alkali metal or alkaline earth metal salicylate represented by the general formula (1) and/or a (per)basic salt thereof:
• R 1 and R 2 may be the same or different and each represent a hydrocarbon group having 1 to 40 carbon atoms, the hydrocarbon group may contain oxygen or nitrogen, M represents an alkali metal or alkaline earth metal such as sodium, potassium, calcium and magnesium, and is preferably calcium or magnesium, more desirably calcium, and n is 1 or 2 in accordance with the valence of the metal.
• hydrocarbon group having 1 to 40 carbon atoms examples include alkyl, cycloalkyl, alkenyl, alkyl-substituted cycloalkyl, aryl, alkyl-substituted aryl and arylalkyl groups.
• alkyl groups which have 1 to 40 carbon atoms (and may be linear or branched) such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and triacontyl groups; cycloalkyl groups having 5 to 7 carbon atoms such as cyclopentyl, cyclohexyl and cycloheptyl,
• R 1 can be combined with R 2 without any especial limitation.
• Preferred examples of the combination thereof are the following combination (1) or (2):
• the hydrocarbon group having 10 to 40 carbon atoms is preferably a secondary alkyl group derived from a polymer or copolymer made from ethylene, propylene, butylene or the like and represented by the following general formula (2):
• x and y are each an integer from 0 to 37 and x+y is from 7 to 37; preferably, x and y are each an integer from 0 to 27 and x+y is from 7 to 27; more preferably, x and y are each an integer from 0 to 16 and x+y is from 7 to 16 or x and y are each an integer from 0 to 23 and x+y is from 17 to 23; and in particular preferably, x and y are each an integer from 0 to 15 and x+y is from 11 to 15.
• the hydrocarbon having less than 10 carbon atoms may be an alkyl group having 1 to less than 10 carbon atoms such as a methyl, ethyl, butyl, or t-butyl group, and may contain oxygen or nitrogen.
• An example thereof is a —COOH group.
• t-butyl and methyl groups are preferable and a methyl group is most preferable.
• the process for producing the component (A) is not particularly limited, and a known process disclosed in JP-B-48-35325, JP-B-50-3082 or the like can be used.
• the component (A) can be obtained by using an o-cresol or p-cresol as a starting material to alkylate the p-position or o-position thereof with an olefin having 10 to less than 20 carbon atoms or 20 to 30 carbon atoms, carboxylating the resultant, and further causing the resultant to react with a metal base such as an oxide or hydroxide of an alkali metal or alkaline earth metal or converting the resultant once into an alkali metal salt such as a sodium or potassium salt and then substituting the salt with an alkaline earth metal salt.
• a metal base such as an oxide or hydroxide of an alkali metal or alkaline earth metal or converting the resultant once into an alkali metal salt such as a sodium or potassium salt and then substituting the salt with an alkaline earth
• the component (A) In the case where phenol is used as a starting material, it is advisable to produce the component (A) through steps of using an olefin having 10 to less than 20 carbon atoms or 20 to 30 carbon atoms in an amount of 1.5 to 4 moles, preferably 2 to 3 moles per mole of phenol to conduct alkylation followed by carboxylation (or steps reverse thereto).
• salicylates other than the salicylate represented by the general formula (1) that is, monoalkyl salicylates having 1 to 40 carbon atoms such as 3-alkyl salicylate, 4-alkyl salicylate and 5-alkyl salicylate may be contained as components resulting from impurities in the process of producing the salicylate represented by the general formula (1) or as optional components.
• the constituent ratio thereof is preferably 50% or less by mole, more preferably 30% or less by mole, even more preferably 10% or less by mole, most preferably approximately 0% by mole.
• a composition wherein the generation of a precipitation is suppressed can be obtained when the component (A) is used together with a sulfonate or the like.
• monoalkyl salicylates are not substantially contained.
• the content of monoalkyl salicylate(s) can be decreased by using an olefin in an amount of 2 moles or more per the phenol to conduct alkylation or by separating and removing monoalkyl salicylate(s) from the resultant mono- and di-alkyl salicylate mixture.
• the component (B) in the lubricating oil additive and the lubricating oil composition of the invention is a metal detergent other than any salicylate detergent. That is, examples thereof include alkali metal or alkaline earth metal detergents made of sulfonates, phenates, carboxylates and naphthenates of alkali metal or alkaline earth metals. In the invention, one or more alkali metal or alkaline earth metal detergents can be used which are selected from the group consisting of the above. Alkaline earth metal sulfonate detergents and alkaline earth metal phenate detergents, in particular, alkaline earth metal sulfonate detergents are preferably used.
• the alkaline earth metals are each an alkaline earth metal salt, in particular, a magnesium salt and/or a calcium salt of an alkyl aromatic sulfonic acid obtained by sulfonating an alkyl aromatic compound having a molecular weight of 300 to 1500, preferably 400 to 700, and the calcium salt is preferably used.
• alkyl aromatic sulfonic acid examples include petroleum sulfonic acid and synthetic sulfonic acid.
• the petroleum sulfonic acid there is generally used a sulfonated alkyl aromatic compound of a lubricant fraction of mineral oil or the so-called mahogany acid, which is produced as a byproduct when white oil is produced.
• the synthetic sulfonic acid there is used, for example, a sulfonated alkylbenzene having a linear or branched alkyl group, which is obtained by alkylating benzene with an oligomer of an olefin having 2 to 12 carbon atoms (such as ethylene or propylene), or a product obtained by sulfonating an alkylnaphthalene such as dinonylnaphthalene.
• the sulfonating agent used when these alkyl aromatic compounds are sulfonated is not limited to any especial kind. Usually, fuming sulfuric acid or sulfuric anhydride is used.
• alkaline earth metal phenates examples include alkaline earth metal salts, in particular, magnesium and calcium salts of Mannich reactants of alkyl phenol, alkylphenol sulfide or alkylphenol. Specific examples thereof include substances represented by the following formulae (3), (4) and (5):
• R 21 , R 22 , R 23 , R 24 , R 25 and R 26 may be the same or different and each represent a linear or branched alkyl group having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, and M 1 , M 2 and M 3 each represent an alkaline earth metal, preferably calcium or magnesium, and x represents 1 or 2.
• R 21 , R 22 , R 23 , R 24 , R 25 and R 26 which are each independent, include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and triacontyl groups. These may be linear or branched. These may also be primaryl alkyl, secondary alkyl or tertiary alkyl groups.
• Examples of the component (A) and component (B) of the invention include not only neutral salts as described above but also basic salts obtained by heating these neutral salts together with an excessive amount of an alkali metal or alkaline earth metal salt or an alkali metal or alkaline earth metal base (a hydroxide or oxide of an alkali metal or alkaline earth metal) in the presence of water; and perbasic salts obtained by causing the neutral salts to react with a base such as a hydroxide of an alkali metal or alkaline earth metal in the presence of carbon dioxide gas, boric acid or a borate.
• a base such as a hydroxide of an alkali metal or alkaline earth metal in the presence of carbon dioxide gas, boric acid or a borate.
• the metal ratio of the component (A) or component (B) is not particularly limited, and the component (A) and component (B) having a metal ratio of 1 to 40, preferably 1 to 20 can be used.
• the metal ratio of the component (A) is 1.1 or more, preferably 1.5 or more, in particular preferably 2.3 or more, and is preferably 10 or less, more preferably 6 or less since the salicylate which may generate a precipitation is a monoalkyl salicylate made into a (per)base with calcium carbonate or the like.
• the component (A) having a metal ratio within such a range is very useful.
• the metal ratio referred to herein is represented by (the valence of the metal element in an alkali metal or alkaline earth metal salicylate, an alkali metal or alkaline earth metal sulfonate, or the like) ⁇ (content (% by mole) of the metal element therein/(content (% by mole) of the soap group therein).
• the metal element means calcium, magnesium or the like
• the soap group means the alkylsalicylic acid group, the alkylsulfonic acid group, or the like.
• the contents of the component (A) and the component (B) are not particularly limited, and are decided as the needs arise for a lubricating oil additive or a lubricating oil product.
• the lower limit of each of the contents is 0.01% by mass, preferably 0.1% by mass of the whole of the composition.
• the upper limit thereof is 40% by mass, preferably 20% by mass, in particular preferably 10% or less by mass.
• the amount of the component (A) is 5% or less by mass, preferably 1% or less by mass, more preferably 0.5% or less by mass, even more preferably 0.3% or less by mass of the whole of the lubricating oil composition
• the amount of the component (B) is 5% or less by mass, preferably 1% or less by mass, more preferably 0.5% or less by mass, even more preferably 0.3% or less by mass, most preferably 0.15% or less by mass of the whole of the lubricating oil composition, these amounts being in terms of the amounts of the alkali metal or alkaline earth metal element.
• the component (B) in particular, a sulfonate having a metal ratio of 2 or less
• the component is incorporated preferably in an amount of 0.08% or less by mass, in particular preferably in an amount of 0.05% or less by mass since the content of the soap group (such as sulfonic acid) becomes relatively high.
• the lubricating oil additive and the lubricating oil composition of the invention are a lubricating oil additive and a lubricating oil composition wherein the component (A) and the component (B) are incorporated into a lubricant base oil, and are good in not only storage stability but also high-temperature detergency, base number maintainability, oxidization stability and others.
• one or more additives may be arbitrarily incorporated thereinto, the additives being selected from (C) an anti-wear agent, (D) an ashless dispersing agent, and (E) an antioxidant, or from known additives such as a friction modifier, a viscosity index improver, a corrosion inhibitor, a rust inhibitor, an anti-emulsifier, a metal inactivator, an antifoaming agent, and a colorant.
• the resultant composition can be supplied as an additive package or lubricating oil product into which these are incorporated.
• anti-wear agent (C) examples include sulfur-containing compounds such as zinc dithiophosphate, zinc dithiocarbamate, thiophosphoric acid esters, disulfides, olefin sulfides, and oil and fat sulfides; monoesters or diesters of phosphorous acid or phosphoric acid, metal (such as zinc) salts thereof, and amine salts thereof; and triesters of phosphorous acid or phosphoric acid. These may be incorporated usually at a ratio of 0.1 to 20% by mass, preferably at a ratio of 0.2 to 10% by mass.
• the component (A) in the invention less easily hinders the effect of the anti-wear agent (C) than any monoalkyl type salicylate; therefore, when the component (C) is used in the lubricating oil composition of the invention, the content thereof can be decreased.
• the amount of the agent (C) can be 0.2% or less by mass, preferably 0.15% or less by mass of the whole of the lubricating oil composition, the amount being in terms of the amount of the sulfur element therein.
• the amount of the agent (C) can be 0.08% or less by mass, more restrictedly 0.05% or less by mass of the whole of the lubricating oil composition, the amount being in terms of the amount of the phosphorus element therein.
• Such a case is useful when the composition of the invention is used as a lubricating oil composition for internal combustion engine. This is because a bad effect thereof onto an exhaust gas purifying catalyst can be decreased.
• Examples of the ashless dispersing agent (D) include succinimide ashless dispersing agents, benzylamine ashless dispersing agents, polybutenylamine ashless dispersing agents, and compounds obtained by modifying these compounds with a boron compound, a oxygen-containing organic compound, a phosphorus compound, a sulfur compound or the like. These may be incorporated usually at a ratio of 0.1 to 20% by mass, preferably at a ratio of 0.5 to 10% by mass.
• any antioxidant that is ordinarily used in lubricating oil can be used, examples thereof including phenol type antioxidants such as 2,6-di-tert-butyl-4-methylphenol, 4,4′-methylenebis(2,6-di-tert-butylphenol), octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and octyl-3-(3-methyl-5-tert-butyl-4-hydroxyphenyl)propionate, amine type antioxidants such as phenyl- ⁇ -naphthylamine, alkylphenyl- ⁇ -naphthylamine, and dialkyldiphenylamine, and metal type antioxidants such as molybdenum and copper antioxidants. These may be incorporated usually at a ratio of 0.1 to 10% by mass, preferably at a ratio of 0.1 to 5% by mass.
• phenol type antioxidants such as 2,6-di-tert-butyl-4
• friction modifier examples include molybdenum dithiophosphate, molybdenum dithiocarbamate, aliphatic acid esters, aliphatic amines, aliphatic amides, and aliphatic ethers.
• the viscosity index improver include the so-called non-dispersion type viscosity index improvers, which are polymers or copolymers made from one or more monomers selected from various methacrylic acid esters, or hydrogenated products thereof; the so-called dispersion type viscosity index improvers, which are obtained by copolymerizing them further with various methacrylic acid esters containing a nitrogen compound; non-dispersion type or dispersion type ethylene/ ⁇ -olefin copolymers (examples of the ⁇ -olefin including propylene, 1-butene and 1-pentene), or hydrogenated products thereof; polyisobutylene, or hydrogenated products thereof; hydrogenated products of styrene/diene copolymer; styrene/anhydrous maleic acid ester copolymer; and polyalkylstyrene.
• non-dispersion type viscosity index improvers which are polymers or copolymers made from one
• the molecular weight of these viscosity index improvers is selected, considering shear stability.
• the number-average molecular weight of the viscosity index improvers is usually from 5,000 to 1,000,000, preferably from 100,000 to 900,000 in the case of, for example, the dispersion type and the non-dispersion type polymethacrylates; is usually from 800 to 5,000, preferably from 1,000 to 4,000 in the case of the polyisobutylene or the hydrogenated products thereof; and is usually from 800 to 500,000, preferably from 3,000 to 200,000 in the case of the ethylene/ ⁇ -olefin copolymers or the hydrogenated products thereof.
• a lubricating oil additive and a lubricating oil composition particularly good in shear stability can be obtained.
• One or more compounds selected at will from the above-mentioned viscosity index improvers can be contained in an arbitrary amount.
• corrosion inhibitor examples include benztriazole type, tolyltriazole type, thiadiazole type, and imidazole type compounds.
• rust inhibitor examples include petroleum sulfonate, alkylbenzenesulfonate, dinonylnaphthalenesulfonate, alkenylsuccinic acid esters, and polyhydric alcohol esters.
• anti-emulsifier examples include polyalkylene glycol type nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether and polyoxyethylene alkyl naphthyl ether.
• metal inactivator examples include imidazolin, pyrimidine derivatives, alkylthiadiazole, mercaptobenzothiazole, benzotriazole or derivatives thereof,
• antifoamer examples include silicone, fluorosilicone, and fluoroalkyl ether.
• these additives are incorporated into the lubricating oil additive of the invention, these additives can be appropriately added in accordance with the use purpose of a lubricating oil composition wherein the lubricating oil additive is to be used, so as to construct the so-called additive package.
• the content thereof is usually selected from the range of 0.1 to 5% by mass of the whole of the lubricating oil composition in the case of the friction modifier, from the range of 0.1 to 20% by mass thereof in the case of the viscosity index improver, from the range of 0.005 to 5% by mass thereof in the case of the corrosion inhibitor, the rust inhibitor or the anti-emulsifier, form the range of 0.005 to 1% by mass thereof in the case of the metal inactivator, and from the range of 0.0005 to 1% by mass thereof in the case of the antifoamer.
• lubricating oil compositions of the invention (Examples 1 to 8) and lubricating oil compositions for comparison (Comparative Examples 1 to 8) were each prepared.
• Example 1 Example 2
• Example 3 Example 4
• Example 5 Example 6
• Example 7 Hydro-refined mineral oil 1) % by mass Balance Balance Balance Solvent refined mineral oil 2) % by mass Balance Balance Balance Perbasic Ca monoalkylsalicylate 1 3) % by mass — — — — — — — — Amount in terms of the alkaline earth % by mass — — — — — — — metal element
• Perbasic Ca monoalkylsalicylate 2 4) % by mass — — — — — — — Amount in terms of the alkaline earth % by mass — — — — — — metal element
• A Perbasic Ca 3-alkyl-5-methylsalicylate % by mass 4 4 2.5 2.5 — — — — — 5)
• a volume of 100 mL of each of the resultants lubricating oil compositions was put into a graduated test tube for centrifugation (see, for example, JIS K 2601), and the following cycle test was made: 0° C. for one week ⁇ 60° C. for 1 week ⁇ 0° C. for 1 week ⁇ 60° C. for 1 week. It was checked with the naked eye whether or not a precipitation was generated.
• Lubricating oil compositions of Examples 1 to 8 according to the invention were each a composition obtained by incorporating, into a lubricant base oil, calcium-carbonate-perbasic calcium (3-alkyl-5-methyl)salicylate or calcium (3,5-dialkyl)salicylate having a metal ratio of 2.7 as a component (A), calcium-carbonate-perbasic calcium sulfonate having a metal ratio of 1 or 10 as a component (B), (C) zinc dithiophosphate, (D) succinimide, (E) phenol type and amine type antioxidants, a viscosity index improver, and an anti-emulsifier.
• a lubricant base oil calcium-carbonate-perbasic calcium (3-alkyl-5-methyl)salicylate or calcium (3,5-dialkyl)salicylate having a metal ratio of 2.7 as a component (A), calcium-carbonate-perbasic calcium sulfonate having a metal ratio of 1 or 10 as
• the lubricating oil additive and the lubricating oil composition of the present invention generate no precipitation and have good storage stability. It has been become possible to supply a lubricating oil additive product or a lubricating oil composition product made of a combination of a (per)basic salicylate and a metal detergent such as (neutral) sulfonate, which has generated a precipitation so as not to be circulated as a product so far or so as to cause a trouble even if it has been circulated.
• the lubricating oil additive and the lubricating oil composition of the invention are useful as a lubricating oil additive or a lubricating oil composition, and can be preferably used as a lubricating oil additive and a lubricating oil composition for internal combustion engines such as gasoline engines, diesel engines and gas engines for two-wheeled vehicles, four-wheeled vehicles, power generation, ships or the like, in particular, a lubricating oil additive and a lubricating oil composition for internal combustion engines using low-sulfur fuels (for example, gasoline, light oil, natural gas and LPG which have a sulfur content of 50 ppm or less by mass, preferably 10 ppm or less by mass, or hydrogen, dimethyl ether (DME), gas-to-liquid (GTL) fuels (light oil fractions and gasoline fractions) and alcohol fuel which do not substantially contain sulfur) since long-drain performance can be made higher.
• low-sulfur fuels for example, gasoline, light oil, natural gas and LPG which have a sulfur content
• the lubricating oil additive and the lubricating oil composition of the invention can be preferably used as a lubricating oil about which storage stability, high-temperature detergency and oxidation stability as described above are required, for example, a lubricating oil for a driving system such as an automatic or manual transmission, or a lubricating oil such as grease, wet brake oil, hydraulic oil, turbine oil, compressor oil, shaft bearing oil or refrigerator oil, and as an additive used therein.

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• 2003
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